Green Light
for Biodiesel
Contents
2 Evonik. Power to create.
3 Innovations for the world of tomorrow 4 Biodiesel
Green light for a future-oriented fuel 6 Rapeseed, Soy & Co.
The source material 7 Transesterification
From vegetable oil to high-tech fuel 8 Alkoxides
High-performance catalysts in the transesterification process
10 Defoamers
A winning team in each additive packet 13 Cold Flow Improvers
Superior at every temperature 16 Special polyamide 12 compounds Paving the way for the new generation of fuels
18 Process Technology & Engineering
Specialists for your special needs 19 Certification
The promise of quality - in writing
Evonik
Evonik is the creative industrial
group from Germany with business
activities all over the world. It is
managed with courage and
deter-mination. To create our own
per-spectives, we leave the beaten path
and win over new markets with
groundbreaking ideas.
Innovations for the world
of tomorrow
Evonik Industries is one of the
worldwide leading companies in
specialty chemicals. The company’s
six business units possess a broad
product portfolio – from synthetic
building blocks to superabsorbents,
from high-performance plastics to
additives for petroleum- or natural
oil-based fuels. With 34,000
employ-ees worldwide, we operate our own
production plants in some thirty
coun-tries, and generate more than 80
percent of our sales from a
market-leading position.
Specialty chemicals are the base
materials of today’s product
innova-tions. The investments we make
year after year in research and
devel-opment are extraordinary. As are the
results. About 20 percent of our
chemical sales are made with products
and applications that are less than five
years old. They ensure our strong
position in the fiercely competitive
specialty chemicals market. And
guar-antee you growing added value and
the competitive advantage so often
decisive today in your markets.
17
Biodiesel
Green light for a future-oriented fuel
The search for alternative sources of energy is a megatrend that will have a
permanent impact on the developments of the coming years and decades.
Many chemical companies, not to mention legislators, have aligned their
strate-gies accordingly. Among the many controversial energy sources out there, and
those that are still in the development stage, one has long since pulled away
from the pack: biodiesel. In many countries, this environmentally friendly fuel
is already a mandatory addition to mineral diesel. With increasing percentages,
biodiesel promises increased climate protection and less reliance on imports.
We’re committed to this promising growth market – with our capabilities as a worldwide leader in specialty chemi-cals, our innovative drive as a visionary supplier of customer-oriented solutions, and our ambition to create sustainable value. We’ve been actively involved in biodiesel ever since commercial produc-tion began.
Today, our knowledge and achievements in the area put us at the forefront of continued development and growth. Our biodiesel portfolio covers a broad spectrum of outstanding products, de-signed for producing and using this “green” fuel:
• Alkoxides as catalysts for efficient transesterification
• Defoamers for effective use in multi- functional diesel additive packages
• Cold Flow Improvers for outstanding low-temperature properties in any region, and any season
• Special polyamide 12 for adapting automotive components to biodiesel
• Process technology consulting services in all related areas of expertise
The net result: solutions that clearly po-sition biodiesel as a viable, high-quality, high-tech fuel – even for today’s diesel engine generations with common rail or unit injector injection systems.
The molecular structure of vegetable oils in their pure form precludes their use
for conventional combustion diesel engines. Vegetable oils – just as animal fats –
consist of triglycerides, that is, the combination of the trivalent alcohol glycerol
with three fatty acids.
The key is to replace the trivalent glycerol with a monovalent methanol. This trans-forms the viscous vegetable oil into a fuel with excellent flow characteristics: biodiesel.
And all it takes is a simple chemical re-action called transesterification, which involves mixing methanol with a small quantity of an alkaline catalyst. Here, sodium methylate 30% solution in methanol (NM 30) and potassium methylate 32% solution in methanol (KM 32) from Evonik have become the industry’s preferred choice.
The quality of the vegetable oil deter-mines the efficacy and cost-efficiency of these catalysts. To prevent undesired side effects, such as soap formation, or increased catalyst consumption, the crude oil should be refined to a water content of max. 0.1% and a free fatty acid (FFA) content of max. 1% preferably 0.1%. In addition to biodiesel, transesterifica-tion also yields glycerol as a valuable by-product for the pharmaceutical and cosmetics industry.
Biodiesel, Ecodiesel, Diesel-Bi – these are just some of the names out there for a
non-petroleum diesel fuel with increasing significance worldwide, especially as an admixture in
fossil diesel. Its chemical term is FAME* and it’s created from native vegetable oils or
animals fats, as well as recycled cooking oils.
*Fatty Acid Methyl Ester
Soy from North and South America, rapeseed from Europe, palm oil from Asia are the most important raw material sources for the biodiesel industry. Animal fats and recycled cooking oils are also used. Recently, more focus has also been placed on second-generation raw materials (jatropha and algae oil). Vegetable oils are converted at a 1:1 proportion to the corresponding methyl esters. These native oils are outstanding starting materials for biodiesel. The biofuel obtained from them stands out for the following properties:
• Very good inherent lubricity
• Lower particulate matter, carbon monoxide and hydrocarbon emissions
• Almost sulfur-free
• Biodegradable, non-toxic
• Recommended for use in water protection areas
Rapeseed, Soy & Co. - the raw material
From vegetable oil to high-tech fuel:
transesterification
(fatty acid methyl esters) (glycerol)
(methanol) (triglycerides)
NM 30 and KM 32: the leading catalysts
Sodium methylate 30% solution in meth-anol (NM 30) is the leading component in the transesterification of vegetable oils. Approximately two-thirds of the capacity of large-scale production plants (50,000 to 1 million metric tons/year) is set up for this catalyst, and continues to grow. For processes using raw material with an FFA* content of more than 1.0%, such as used cooking oils or animal fats, Evonik proposes potassium methylate 32% solution in methanol (KM 32). Both catalysts can be used in anhydrous production processes and directly from the storage tank – in a closed circuit and without any additional intermediary steps. This reduces handling risks to an abso-lute minimum.
Alkoxide catalysts NM 30 and KM 32 are also the preferred choice because of their cost-efficiency. Supplied ready for use, they save an entire production step in the making of biodiesel fuel that would otherwise be required for dissolving the catalyst in the methanol. The powerful alkoxides from Evonik also pay off by in-creasing biodiesel yields by 2 to 5%, and generating higher-purity glycerol. The latter is actually obtained with a technical purity of 80–85%. The higher purity makes an important contribution to the cost-effectiveness of a biodiesel plant. *Free fatty acids
Service: expect a lot
Biodiesel catalysts from Evonik are backed by the roughly 40 years of expertise in manufacturing alkoxides, plus more than 17 years of experience in addressing vari-ous challenges of the biodiesel industry. They are also the result of significant in-vestments in research and development, especially with a focus on biodiesel based on promising second-generation raw materials, such as jatropha or algae oil. But most importantly, behind our market-leading alkoxides you have the minds of the people at Evonik, who are excited about their work, and support you with knowledge and experience –whether in application engineering, specification-compliant production of biodiesel, or optimizing production facilities. The analytical lab of Evonik, with all its technical facilities, from chromatography to titration and more fuel related analy-ses, is also at your disposal to make your product meet all relevant specifications.
Proximity: the advantage of a global partner
Proximity to your production facility is an important advantage – not only because you may sometimes need to address urgent bottlenecks. As a global player, we’re in 50 countries around the world, and everywhere in the Americas, Asia, and Europe. This not only means outstanding availability and short lead time, but also that we speak your lan-guage – regardless of where your bio-diesel plant is located.
Alkoxides have been used to transesterify vegetable oils since 1852. With the
growing importance of biodiesel, the process has been optimized to the extent
that now various raw vegetable oils can be transesterified to biodiesel and
glycerol with higher yields and better product quality. Here alkoxides from
Evonik are making the difference. As the worlds leading producer of specialized
intermediates, we offer advanced catalyst solutions specifically designed to
ad-dress the requirements of producing biofuels. The added value: high yield,
simple, safe handling in a closed circuit combined with significant gains in
effi-ciency and productivity.
8 9
Alkoxides
High-performance catalysts in
the transesterification process
New innovation: defoaming B7 diesel
The latest member of our diesel defoamer family is
TEGO® Antifoam MR 507. This product is especially de-signed to defoam diesel fuels with high amounts of bio components regardless of their individual raw material source.
Know-how: the key to successful innovation For more than 3 decades Evonik Industries has been supplying formulators of the diesel market with superior solutions in the field of de-foaming. Being a think-tank with proprietary access to broad technology platforms, we have emerged to become a unique supplier offering in-novative products. With our formulating experience and your knowledge in the market we help you to develop your next product generation.
We nurture long-standing de-velopment partnerships with leading package manufacturers and work closely together with universities and research insti-tutes, delving even deeper into effective foam inhibition. Our goal remains unchanged: to make tomorrow’s defoamers even more efficient and more effective for use in multifunc-tional diesel additive packages.
TEGO® Antifoam: tailored foam brakes
TEGO® Antifoam is a family of high-performance defoamers for diesel fuels and biodiesel blends. Based on the latest organo modified siloxane technology, these products are tailored for diverse diesel qualities and additive combinations. TEGO® Antifoam defoamers provide excellent properties: long time performance, package stability, and solvent compatibility.
They are also characterized by outstanding results which they achieve in BNP and filtration tests. Here,
TEGO® Antifoam MR 465 and MR 467 lead the charts. Highly effective in both dry (low lubricity) and wet diesel, they unfold their defoaming action in concentrations as low as 4–6ppm, in most cases without requiring additional solvents. TEGO® Antifoam MR 467 currently sets the efficacy and efficiency standards for advanced high-performance diesel with a cetane index above 60. We offer
TEGOPREN® 5851 as a cost-effective alternative for use with mainly dry diesel.
Active ingredient: built-in efficiency Cost-effectiveness is a primary focus in the development of our defoamers – accepting no compromise of performance. The result: TEGO® Antifoam defoamers are highly active even at low dosages. Particularly for wet diesel they deliver significant benefits in terms of foam height and collapse time. And they significantly reduce the requirement for other additive components, such as solvents. TEGO® Antifoam products are able to reduce the solvent content by up to 30%.
Service: flexibility at your command
Because we are the leading supplier of defoamers, you can expect more from us than excellent products. Our mutual beneficial concepts of partnerships spark innovative solutions in applied laboratory and R&D projects. Our service includes final specificationchecks as well as BNP test series of your DAPs.
Defoamers
A winning team in every additive package
Excessive foaming, reduced filling capacity, longer filling times, and thus reduced productivity at
the fuel pump – these are the main reasons why defoamers have become a key component in
multifunctional diesel additive packages (DAP). And yet the requirements of defoamers today
are anything but standard. Additive packages are constantly being adapted to new specifications
to extract more energy from fuels – and to maintain their effectiveness with every new engine
generation and further reduce emissions. That’s why defoamers are being constantly refined for
better performance and greater cost-effectiveness. Defoamers that meet these demands are
known under the brand name TEGO® Antifoam.
Defoaming performance is measured in foam height and collapse time. The standard BNP foam test proves that TEGO® Antifoam MR 507 yield to outstanding efficacy over time. For the following standard foam test (BNP test) we used B7 diesel.
TEGO® Antifoam defoamers are based on organomodified siloxanes. The silox-ane backbone ensures low surface ten-sion - one of the prerequisites for an ef-fective foam inhibitor. The specific design of the organic ligands translates into improved stability and compatibility.
Foam height [ ml ]
Testtime [ days ] without defoamer with TEGO® Antifoam MR 467 with TEGO® Antifoam MR 507
Foam collape time [ sec ]
Testtime [ days ] without defoamer with TEGO® Antifoam MR 467 with TEGO® Antifoam MR 507 Treatrate for both products 6ppm Treatrate for both products 6ppm
12
The cold: a challenge for biodiesel As liquid biodiesel is cooled, the compo-nents with a higher melting point begin to crystallize and come out of the solution. Initially, they form small crystals, which make the fuel look hazy to the naked eye. The temperature at which this first occurs is called the Cloud Point (CP). Continued cooling causes the crystals to grow into plate and needle structures that increase the viscosity of the biodiesel. When these plate and needle structures become suffi-ciently large; however, they can cause filter plugging, with the temperature at which this occurs being the Cold Filter Plugging Point (CFPP).
With further cooling, the crystals will continue to grow and form a three-dimen-sional lattice structure, which traps and immobilizes the biodiesel components that are still in the liquid phase. The lowest temperature at which fuel is still flowing is known as the Pour Point (PP). CP, CFPP and PP can be very close together in the untreated Biodiesel.
When the fuel is stored at a temperature between its Cloud Point and its Pour Point and the crystallization process is left un-disturbed, waxy structures can settle out as a visible lower layer with a more or less diffuse structure. This wax formation and sedimentation process can be a source of extreme handling problems during storage and transport, but can be lessened in severity, or even eliminated, with the use of Cold Flow Improvers.
Biodiesel fuels have different flow properties in cold temperatures.
The reason is that biodiesel is made up of various long-chain fatty
acid methyl esters (FAMEs). Because their melting points vary
within a broad range of about -35 to +45°C, the low-temperature
properties of the biofuel can be adversely affected, depending on
whether it’s based on soybean, rapeseed, palm oil or animal tallow.
The leading solution for this problem is VISCOPLEX® Cold Flow
Improvers (CFIs), a broad spectrum of Cold Flow Improvers from
the Evonik Oil Additives Business Line of Evonik Industries. They
provide outstanding flow properties for your biofuel - in any region
or season. And they mean superior cost-efficiency when it comes to
ensuring that different types of biodiesel meet the low-temperature
performance standards of current fuel specifications.
13
Cold Flow Improvers
Superior at any temperature
VISCOPLEX® CFIs: trademark of leading
solutions
The operating principle of tailored VISCOPLEX® CFIs is based on its ability to nucleate and to co-crystallize on the edges of the growing crystal plates, thereby effectively blocking the continued growth of the individual crystal. The result is smaller crystals that more easily pass filters and that are less able to form the three-dimensional gel structures. The impact on the flow properties at cold temperatures: a drastic improvement in CFPP, PP and Filterability. Also the CP can be reduced by up to 6°C in FAME blends.
untreated
Crystals > 50µm Crystals < 5µmwith VISCoplEx®
Cloud point CFpp* pour point T [°C] Cloud point CFpp* pour point Large agglomerated crystals Small dispersed crystals TME/SME 30/70 TME/SME 30/70*CFPP = Cold Filter Plugging Point
Worldwide expertise: the security of a global player
Evonik Oil Additives is the global leader in improv-ing the cold flow properties of a wide range of pe-troleum and natural oil-based fuels and lubricants. Under the trademark of VISCOPLEX®, we develop, produce and market viscosity index improvers, pour point depressants, dewaxing aids for refineries and special Cold Flow Improvers for biodiesel. We also support you with tailor-made products and ser-vices that meet your critical and specific demands for effective and economical solutions – worldwide.
Backed by highly trained experts and state-of-the-art technology centers in North America, Europe and Asia, we have 60 years of expertise, and proprie-tary polymer technology produced by a worldwide manufacturing network to guarantee you the quality in product, supply and availability that you expect from a global market leader.
To obtain a sample, find your local Evonik Oil Additives contact at www.evonik.com/oil-additives.
The use of VISCOPLEX® CFIs has often proven more eco-nomical than other means for meeting the necessary CFPP requirements. In FAME-type blends, the use of VISCOPLEX® CFIs, if correctly selected, will reduce the quantity of costly FAMEs. In most cases, the savings in the cost of FAMEs more than pays for the cost of the Cold Flow Improver. Contact us to discuss our expe-rience with blends of soybean with animal tallow or rapeseed. Increasing the Value
of FAMEs by Blending and Additization: Focus on Biodiesel with CFPP = +10°C: Less expensive TME can be blended in higher proportions by use of VISCOPLEX® CFI.
Cost Saving with VISCOPLEX® in TME-SME Blends (Txx) 20 15 10 5 0 -5 -10 0 10 20 30 40 50 60 70 80 90 100 pure pure
SoyME Fraction of TallowME [%] TallowME
CFP
P [
°C
]
non-additized treated with VISCOPLEX®
Cost Optimization with VISCOPLEX® CFI
VISCOPLEX® Improves Cold Storage of Biodiesel
Biodiesel Samples Stored at – 5 (Soy) and +3°C (T25) for 72 hours
Fuel Soy ME*
T25
(75% SoyME + 25% TallowME)*
Parameter CP [°C] CFFP [°C] picture CP [°C] CFFP [°C] picture
untreated -2 -3 9 3
+ VISCOPLEX® -5 -9 3 -2
*ME = Methyl Ester
VISCOPLEX® 10-series – Our Biodiesel CFI Portfolio
Optimal Solutions for all Temperatures 10-605
10-505
Canola, Rapeseed Soybean Blends with Tallow or palm Tallow/palm
10-510 10-330
10-502 10-530
10-340
Min. Application Temperature of Biodiesel [°C]
VESTAMID®: the brand of choice for
highly stable line systems
Polyamide 12 compounds from Evonik are synonymous with quality in the auto-motive and supplier industries. Marketed under the VESTAMID® brand, they’ve been the preferred choice for fuel line applications at renowned manufacturers for over 30 years.
VESTAMID® owes its status as the most popular polyamide 12 compound in the automotive industry to the consistently high level of quality, as well as such fac-tors as excellent service, reliable delivery, and innovative solutions.
The most recent examples in the product family, VESTAMID® LX9008 and LX9013, have proven outstanding when used with RME biodiesel blends. As shown in tests according to the tough SAE J2260 stan-dards in the US, this compound designed for the new diesel engine generations with common-rail or pump-nozzle systems is not only more resistant to aging under higher pressures and constant operating temperatures of 125°C, but also signifi-cantly more resistant to the free radicals that form in biofuels and can lead to a break-up of polymer chains.
Service: creating the competitive edge
With VESTAMID® LX9008 and LX9013, Evonik delivers clear competitive advan-tages, including technical superiority and significantly higher cost-effectiveness compared, for instance, to vulcanized elastomer compounds.
In addition, Evonik provides a modified VESTAMID® grade for an especially developed two-layer fuel line system called MLT 7040 (Multi-Layer Tube). Its conductive inner layer consists of a barrier material and, among others, pro-tects the outer polymer against possibly aggressive substances in different biofuels. Time and again, our strong focus on in-novative solutions delivers a competitive advantage for our customers. Approxi-mately 6% of sales of the High Perfor-mance Polymers Business Line goes back into research and development. No fewer than one-fifth of the roughly 1,000 people here work on developing new products and optimizing standard products, for current and coming gener-ations of automobiles.
Ultimately, our approach to service translates into a competitive advantage for our customers – as does our proximity to where the rubber meets the road. It comes from working closely together with suppliers, systems developers, and automotive manufacturers.
Together, we exchange news and views and trends in compound development, testing technology, and legislation. Together we tailor special polyamide 12 compound to special applications, we design and define molds and tools, we keep manufacturing-technology personnel up to speed, and we develop new testing methods. More often than not, our processes eventually become industry standards. Our commitment to establishing standards gives you the re-assurance of quick reaction to change.
Special polyamide 12 compound
Clearing the way for the new fuel generation
Currently, B100-grade biodiesel may be used only if manufacturers
expressly designate their vehicles as being compatible with this pure
form of biodiesel. There’s a good reason for this restriction. The solvent
nature of certain chemical properties in biofuel can damage plastic and
rubber components in the engine and fuel systems. All current tests
have proven the aging resistance of special polyamide 12 compounds
designed specifically for the automotive fuel systems of engines
com-patible with biodiesel blends based on rapeseed methyl esters.
18
Total Quality is the connective tissue that runs through all our activities at Evonik. This applies to all our sites around the world, and all our business units. From raw material selection to production to delivery, the entire manufacturing process for our special solutions for biodiesel is reverse integrated.
Quality assurance is thus the responsibility of each business unit–and the best guarantee for consistent quality, homogeneous processes, and product properties, as well as excellent delivery reliability. We’ll give it to you in writing.
process Technology & Engineering
Specialists for technology needs
As a global operator and the worldwide leader in specialty chemicals, Evonik draws on a wealth
of experience in process technology. We pool and network this knowledge in our Process
Tech-nology & Engineering unit.
Our services and solutions, often developed jointly with research institutes and universities, form
the basis for developing new technologies, methods and processes – as well as for further
process and cost optimization. We support our business units to achieve their goals in the
biodiesel field - from solving problems in biodiesel production all the way to cost-effective
capacity expansion for the growing biofuel market.
Process Technology: the know-how for improving plant and equipment efficiency
Process optimization is a key aspect of our work in the biodiesel field. We help to make existing biodiesel facilities more cost-effective and more produc-tive. Our competency areas cover the use of new oils and the optimization of existing reaction and separation stages in the biodiesel process as well as elimi-nating bottlenecks in existing plants to achieve 20 to 30% capacity gains. Throughout these projects we support our business units with interdisciplinary teams that cover all the bases, from solution development and pre-selection to testing in our laboratories or pilot plants – all the way to successful large-scale implementation.
Engineering: international experience in plant design and construction The core competency of Engineering lies in the planning and construction of production plants – in Germany and abroad. In the field of biodiesel, we focus on optimization measures such as eliminating bottlenecks. Our range of services for our business units includes:
• Project management, including quality, cost and schedule control
• Planning, including feasibility studies, basic and detail engineering
• Specialized services, from equipment technology to production logistics
• Construction and assembly management, and
• Operational support and training of personnel
Qualified and professional engineers and technicians, experienced in project and plant management, will deliver these services. That’s why our customers can be sure that project objectives will be
Certifications
The promise of quality – in writing
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ISO 9001 ISO 14001 ISO / TS EMAS Kosher
Quality Environmental 169-49:2002 European Certification Management Management Quality Environmental
System System Management Management System System
Alkoxides
Niederkassel-Lülsdorf (G)
Cold Flow Improvers
worldwide Defoamers Essen (G) Special Polyamide 12 Marl (G)
Management-Systems
Disclaimer
This information and all technical and other advice are based on Evonik’s pres-ent knowledge and experience. How-ever, Evonik assumes no liability for such information or advice, including the extent to which such information or ad-vice may relate to third party intellectual property rights. Evonik reserves the right to make any changes to informa-tion or advice at any time, without prior or subsequent notice. EVONIK DIS-CLAIMS ALL REPRESENTATIONS AND WARRANTIES, WHETHER EX-PRESS OR IMPLIED, AND SHALL HAVE NO LIABILITY FOR, MER-CHANTABILITY OF THE PRODUCT OR ITS FITNESS FOR A PARTICULAR PURPOSE (EVEN IF EVONIK IS AWARE OF SUCH PURPOSE), OR OTHERWISE.
EVONIK SHALL NOT BE RESPONSI-BLE FOR CONSEQUENTIAL, INDI-RECT OR INCIDENTAL DAMAGES (INCLUDING LOSS OF PROFITS) OF ANY KIND. It is the customer’s sole re-sponsibility to arrange for inspection and testing of all products by qualified ex-perts. Reference to trade names used by other companies is neither a recommen-dation nor an endorsement of the corre-sponding product, and does not imply that similar products could not be used. (Status: September 2008) Alkoxides: Michael Markolwitz phone +49 2208 69-571 fax +49 2208 69-640 [email protected] Defoamers: Dirk Steinbeck phone +49 201 173-1655 fax +49 201 173-1990 [email protected]
Cold Flow Improvers: Dr. Frank-Olaf Mähling
phone +49 6151 18-4160
fax +49 6151 18-4100
Special Polyamide 12 Compounds:
Dr. Ursula Keil
phone +49 2365 49-9878
fax +49 2365 49-809878
Process Technology & Engineering:
Dr. Mirko Michel
phone +49 2365 49-4651
fax +49 2365 49-804651
[email protected] Confidence in our products and the ability to deliver on our promise starts with the relationship between people. That’s why you’ll have one main contact for each specialized area, one who not only knows the bi-odiesel market inside and out, but also understands your needs and the requirements of your industry down to the smallest detail.
With product knowledge and experience, your contact is there to sup-port you in any and all issues you deal with when it comes to biodiesel and implementing our solutions.
Evonik Industries AG Rellinghauser Straße 1–11 45128 Essen Germany www. evonik.com ic -2 -g b-5 00 -0 1.1 2
